Addition of polyfluoroalkyl iodides to unsaturated compounds and products produced thereby



United States Patent ADDITION OF POLYFLUOROALKYL IODIDES TO UNSATURATEDCOMPOUNDS AND PRODUCTS PRODUCED THEREBY Neal 0. Brace, Wilmington, Del.,assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., acorporation of Delaware No Drawing. .Filed Feb. 23, 1961,.Ser. No.90,911

7 Claims. (Cl. 260-408) This invention is directed to a novel chemicalcomposition and process, said process comprising the free radicalcatalyzed addition of polyfluoroalkyl iodides of structure ACFIB,wherein A and B are chosen from fluorine and Y(C F2n), Y is fluorine,chlorine, bromine or hydrogen and n is from 1 to about 20-, and I(C F)I, wherein r is from 3 to about 20, to hydrocarbon olefins oracetylenes to form products of structure wherein m is an integer,generally equal to one but sometimes larger and only rarely greater thanten. Hydrocarbon olefins or acetylenes may be substituted with a varietyof groups but not a plurality of halogen.

It is well known that polyfluoroalkyl iodides are cleaved to freeradicals by heat or ultraviolet light and that these radicals add toolefins or acetylenes to form products of where m is usually one but maybe larger. It is also known that such reactions are rather timeconsuming and inconvenient on a large scale. For instance, Haszeldine(J. Chem. Soc., 1949, 2856) reports that it takes 108 hours to obtain a46% conversion in the photochemical addition of CF 1 to ethylene and 40hours at 180 C. to obtain a 7% conversion in the thermal addition of CF1 to ethylene. Although these are extreme cases, there are many examplesof such reactions which require extended periods of time. In many cases,the yields of desired products are low because of side reactions,particularly the thermal or photochemical decomposition of the productiodides.

When commercial application of such reactions is considered (for severalproducts which can be prepared by these additions are industriallyuseful), it soon becomes apparent that the photochemical or thermalreactions are not feasible. The size of equipment necessary and rates ofproduction possible make the products obtained too expensive.Photochemical processes, in general, are expensive because of the largeconsumption of electric power. There are recorded instances, also, whenboth the photochemical and thermal processes fail completely.

It is, therefore, an object of the present invention to provide novelchemical compositions and a novel and economical process for reactingpolyfluoroalkyl iodides with hydrocarbon olefins or acetylenes in highconversion and high yield.

3,145,222 Patented Aug. '18, 1964 "ice It is a further object of thisinvention to provide a process whereby products can be prepared whichcannot be prepared by the thermal or photochemical additions to olefins.

These and other objects will become apparent in the followingdescription and claims.

The objects of the present invention have been attained by the discoverythat perfluoroalkyl iodides can be added to olefins in the presence offree-radical generating catalysts to give the addition products in highconversions and yields and that products which cannot be prepared by thethermal or photochemical processes, can be prepared using free radicalcatalysts as follows.

More specifically, the present invention is directed to a compositionhaving the structure Y(C F )Q wherein Y is selected from the groupconsisting of hydrogen, fluorine, chlorine and bromine, n is an integerfrom one to about twenty and Q is selected from the group consisting of(a) CH CHIO CR,

(d) CH CH CH O (CH CO H and (e) --CH=CI(CH CO H wherein R of (a) is alower alkyl group and m of (b), (c), (d) and (e) is an integer of fromzero to about fourteen.

The present invention is also directed to a process for reactingpolyfluoroalkyl iodides with aliphatic olefins and acetylenes to formaddition products which comprises heating polyfluoroalkyl iodides chosenfrom A-CFIB and I(C F )I, where A and B are chosen from fluorine and Y(C2n), Y is chosen from fluorine, chlorine, bromine and hydrogen, n is aninteger of from one to about twenty and r is an integer of from three toabout twenty, with unsaturated compounds chosen from aliphatic olefinsand acetylenes in the presence of a free-radical generating compound attemperatures of from about 50 C. to about 190 C. and from about one toabout 50 atmospheres pressure and recovering the products from thereaction mixture; wherein saidolefins are chosen from Z CH=CZ Z Z and Zare chosen from hydrogen, alkyl, including wherein Z and Z are joinedtogether to form a cyclic aliphatic ring system, chloroalkyl, R--CH=CH-R'OR, R'CO R,

-R'CH(CO alkyl) and R'CO-R'CO R, R is a saturated divalent alkylenebridging group and R is chosen from hydrogen and alkyl, Z is chosen fromthe groups defining Z and Z CO R, -CONR aryl, O CR'CH=CH and -CCl=CHincluding wherein Z and Z are joined together to form a cyclic aliphaticring system, said olefin Z CH=CZ Z containing from two to about thirtycarbon atoms and at least one of Z Z1CECZ2 wherein Z and Z are aspreviously defined O and said acetylene containing from two to thirtycarbon atoms.

Many types of olefins, acetylenes and dienes are useful in the presentprocess. Primarily, the olefins are characterized by having no less thantwo hydrogens attached to the double-bonded carbons; these may both beattached to one carbon or one to each carbon. There is one otherlimitation on the olefins, that no more than one halogen, aryl group orother electronegative group is attached to the double-bonded carbons.The following types of olefins have been used:

"3 /(CdH2d) (cyclohexeue (i=4) CH 5 O/(CJHgs-t) (bicyelohe ptene e=5),CH

u (0 131 (bicycloheptadiene e 5), CH

C Hzzw Hgb) (methylenecyclopropane b 2),

A C (Gb 2b-1Q) (3-cyanomethylenecyclobutano b =3, Q, C N),

ll cash-3Q) (5acetomethoxybicyc1oheptene-2 e=5, Q

CH202CHa) Acetylenes such as C H C H CECH (n=4), HCEC aryl (aryl=C HHCEC(CH CO H (12:0, 8),

RCECR (R=C H Polyfluoroalkyl iodides useful according to the presentinvention have the structures ACFIB and I(C,.F ,)I wherein A and B arefluorine or Y(C F Y is fluorine, chlorine, bromide or hydrogen. Theiodines of I(C,F ,)I are not attached to the same or adjacent carbons.Thus, these iodides include:

The present process may be carried out in either a batch or continuousmanner. While, for small scale preparations, the batch process is moreconvenient, the continuous process is more useful for commercialoperations. The process is carried out at either atmospheric orsuperatmospheric pressure depending on the reactants. If either iodideor olefin have boiling points below the desired reaction temperature, apressure system must be used, otherwise the process may be carried outat atmospheric pressure. If either reactant has a critical temperaturebelow the reaction temperature, e.g., ethylene whose criticaltemperature is 9 C., that reactant will be largely gaseous at thereaction temperature.

The reaction temperature varies'considerably depending on the nature ofthe free-radical generating catalyst being used. Azo catalysts such asalpha,alpha'-azobisisobutyronitrile require relatively low temperaturessuch as 50 to 80 C. (certain acyl peroxides are even lower, e.g., (CH COBenzoyl peroxide requires a. somewhat higher temperature, viz. 80 to 100C., while a dialkyl peroxide such as di-tert-butyl peroxide requires aneven (Y=H, c1 or Br, n=1-19). See Haszeldine, J. Chem.

Soc., 1952, 4259; Brice and Simons, J. Am. Chem. Soc., 73, 4016 (1951).

See Krespan, J. Org. Chem, 23, 2016 (1958).

(Y=F, Cl, Br or H, both not necessarily the same, m and 11%0; seeHaszeldine, J. Chem. Soc., 1949, 2856; 1953, 376; Hauptschein et al., J.Am. Chem. Soc., 79, 2549 (1957)).

v The olefins Y(C F )CF=CF are readily available from the correspondingacids Y(C,,F )CF CF CO H by pyrolysis of the sodium salt. Thus, a widevariety of polyfluoroalkyl iodides are available.

Polyfluoro iodides of type I(C,F )I are available from either The seriesof compounds Br(CF CF I is prepared as follows. One mole of ICF CF Brand a catalytic amount of azobisisobutyronitrile were placed in a shakertube and heated to 80 C. Tetrafluoroethylene (one mole) was added inincrements over a period of several hours. Fractionation of theresulting product gave the following:

Wt. per- Relative Compound B.P./mm. M cent percent of product Analogousresults were obtained with CICF CF I to obtain the series of productsCl(CF CF I.

The products of the present invention are compounds of structure t an t(5'' R I and R -I L1 [.I L .1...

where R is the poly-fiuoroalkyl group. In the great ma- -jority of casesm is one; however, with certain highly reactive olefins or acetylenes, mcan be greater than one, e.g., C5H5CH=CH2, CHZICHCOZC2H5,

COzCHa CH2=C and C H For the most part, it is desirable that m should beone since the products obtained thereby are valuable for a variety ofpurposes. For example, reaction Of C7F15I With. gives which is valuableas .a surface active agent. The iodoacid is readily reduced toC7F15(CH2)mcO2H which is also valuable as a surface active agent.(Australian appln. 38,940, June 24, 1958; Canadian Patent 589,703 andUS. Patent 2,951,051). The reaction of C F I with ethylene may give C FCH CH I under the proper conditions. Reaction of this iodide with sodiummethacrylate gives which forms valuable polymers. The same valuablepolyrrner intermediate may be prepared by reacting C F I with vinylacetate to give reductionof which with zinc and acid gives C F CH CH OHwhich is then esterified with methacrylic acid. Other valuable productsare obtained by reacting CgFqI with fi-pinene, which givesDehydrogenation of this product by standard methods (which isaccompanied by reductive removal of the iodine) gives a valuableperfluoroalkyl-arornatic compound. The addition of C3F7I to allylacetate ,gives C F CH CHICH O CCH which, on hydrolysis and treatmentwith alkali, gives .a valuable polyfluoro epoxy polymer intermediate.The

present process may also be used to prepare valuable perfluoroalkylatedpolymers. Thus, reaction of C F I with Where n is a fairly large number,a water and oil repellent polymer.

The addition of I(C,F ,)I to ethylene gives ICH CH (C F ,)CH CH I whichis readily converted to the valuable diene CH =CH(C,F ,)CH=CH 'oftenused but other methods may be used if the products are not distillable.

When carried out in a continuous system, the reactants and catalyst arefed at a constant rate into an agitated and heated vessel which is keptliquid full. Product leaving the reaction vessel through a pressureregulating device is fractionated and the product collected. Unreactedstarting materials are recycled to the reaction vessel. The pressureused need not be very high, in most cases just sutficient to keep thereactants liquified. If gaseous reactants are involved, theconcentration is adjusted with the pressure.

It is apparent to those skilled in the art that substances whichinterfere with free radical reactions must be avoided in the reactionmixtures. It is particularly important that the perfluoroalkyl iodidesused be free of any molecular iodine.

The following representative examples are given to illustrate thepractice of the present invention and are not intended to limit thescope of the invention. The examples are at atmospheric pressure unlessindicated specifically otherwise.

EXAMPLE 1 A mixture of heptene-l (19.9 g., 0.2 mole),l-iodoperfluoropropane (60.0 g., 0.2 mole) andoz,oc'-aZObiS-n:,'y-dimethylvaleronitrile (0.4 g., 0.0016 mole) washeated under reflux at 55-79 with a nitrogen atmosphere for two hourswhen refluxing stopped. Heating was continued for a further two hours at70-76 C. The clear, colorless product was subjected to fractionaldistillation at 10 mm. pressure giving 64.5 g. (82% conversion) of B.P.86, 11 1.4072. The distillation residue weighed 3.9 g., 11 1.4168.Starting materials (11.9 g., n 1.3595) were collected in a cold trap.Material recovery was 100%.

Analysis.Calcd. for C H F I: C, 30.4; H, 3.56; I, 32.2. Found: C, 30.5;H, 3.8; I, 31.5.

EXAMPLE 2 A mixture of 1,5-hexadiene (8.2 g., 0.1 mole),l-iodoperfluoropropane (60.0 g., 0.2 mole) and a,oc'-aZO-biSu,'y-dimethylvaleronitrile (0.5 g., 0.002 mole) was refluxed for sevenhours at 60-65 C. only (96% conversion to product). Fractionaldistillation of the reaction mixture gave C F CH CHI(CH CH=CH B.P. 56C./ 5 .0 mm., 11 1.4098 (30% conversion) and B.P. 85/0.5 mm., 11 1.4199,M.P. 28 (60% conversion). Unreacted starting materials (13.0 g.) wererecovered in the cold trap.

Analysis of C F- CH CHKCH CH=CH .Calcd. for C H F I: C, 28.6; H, 2.7; F,35.2. Found: C, 28.7; H, 2.7; F, 32.6.

Analysis of CaFqCHgCHI(CH2)2CHICH2C3F7. Calcd. for C H F I C, 21.4; H,1.75; F, 39.5. Found: C, 21.9; H, 1.6; F, 38.0.

EXAMPLE 3 Hexyne-l (9.2 g., 0.1 mole), l-iodoperfluoropropane (39.1 g.,0.132 mole) and u,tad-azobis-a,' -dimethylvaleronitrile (0.2 g., 0.8 m.mole) were heated under reflux at 6270 C. for 6 hours. The reactionproduct was fractionally distilled giving C3F7CH:CI(CH2)3CH3, B.P. 76/20mm., 11 1.4097, 35.8 g. (95% conversion) and 0.5 g. of residue. The coldtrap contained 7.1 g. of starting materials.

Redistillation of C F CH=CI(CH CH gave B.P. 94 C./50 mm., n 1.4097.

Analysis.-Calcd. for C H F Iz C, 28.6; H, 2.67; F, 35.15; I, 33.5.Found: C, 28.8; H, 2.7; F, 35.2; I, 33.0.

The product was shown by analysis of its infrared spectrum to have thetrans configuration between the C3F7 and I groups, bands at 3.22, 3.37,3.45, 6.08 and 10.30,u.

EXAMPLE 4 A mixture of fi-allyloxypropionic acid (0.1 mole), 1-iodoperfluoropropane (0.15 mole) and a,a-azobisisobutyronitrile (4.0rnillimoles) was heated at 50-70 C. for 14 hours giving 86% conversionto product (100% recovery, 95% yield), 11 1.4263.

Analysis.-Calcd. for C H F O I: I, 29.8. I, 27.1.

Found:

EXAMPLE 5 C F CH CHICH OCH CH CO H (35.0 g., 0.082 mole) was allowed tostand at 25 C. for 2 days with 300 ml. of a solution of potassiumhydroxide (15.6 g., 0.28 mole) in alcohol. Acidification of thesolution, dilution with 50 ml. of water, extraction with ether anddistillation gave CHFCHCH OCH CH CO H, B.P. 6682/0.5 mm., 1.4037, 2.2g., and

B.P. 138/10 mm., n 1.3634.

Analysis.Calcd. for C H F O C, 36.0; H, 3.7. Found: C, 36.2; H, 3.3.

In the same manner as Example IV, n-perfluoroheptyl iodide (50 g.),B-allyloxypropionic acid (43 g.) and azobis-isobutyronitrile (0.4 g.)were heated at 90-100" C. for five hOllI'S, in 70% conversion, 111.3969.

Analysis.Calcd. for C H F O I: C, 24.9; H, 1.61; F, 45.6; I, 20.3.Found: C, 26.4; H, 1.85; F, 42.3; I, 19.4.

The above product (43 g.) was treated with potassium hydroxide (10 g.)in ethanol (200 ml.) at 30- 40 for two hours then at room temperatureovernight. The solution was then neutralized (litmus) and the solventevaporated at 300 mm. pressure. Then, 10 ml. of 10% sulfuric acid in ml.of water was added. The mixture was extracted with ether three times.After washing the ether solution with water three times and shaking withmercury to remove iodine, it was dried over magnesium sulfate anddistilled, giving 1.9 g. of forerun and 19.1 g. ofC7F15CH=CHCH20(CH2)2CO2H, B.P. 121/0.5 mm. The redistilled product hadB.P. 3.5 mm., 11 1.3551.

Analysis.-Calcd. for C H F O C, 31.4; H, 1.8; F, 57.2. Found: C, 31.4;H, 1.8; F, 56.9.

In the same manner as above was reduced to C F (CH O(CH CO H, B.P. 113C./O.2 mm., n 1.3491.

9 Analysis.Calcd. for C H F O C, 31.2; H, 2.2; F, 57.0. Found: C, 31.4;H, 2.2; F, 58.0.

Both C F CH CHICH O(CH CO H and C F CH CHIO (CH CO H are surface activeagents. However, since the iodine is somewhat labile, it is better toconvert them to the olefinic or saturated acids for use as surfactants.

Surface tensions of aqueous solutions of as the sodium salt, are asfollows:

Cone. (wt. percent) 0.75 0.38 0.19 0.10 0.05 25 dynes/cm 22.6 25.8 25.126.3 36.5

H2O corrected Surface tensions of aqueous solutions of as the sodiumsalt, are as follows:

Cone. (wt. percent) 0.4 0. 2 1 40.05 0.025 25 dynes/cm 15.7 15.8 15 916.6 17.5

H O corrected Cone. (wt. percent) 0.0125 0.00625 0. 0034 0.0016 0.0007825 dynes/cm 20. 5 21.9 25.0 28.9 34.9

H O corrected Surface tensions of aqueous solutions of as the sodiumsalt, are as follows:

Cone. (wt. percent) 0.8 0.4 0.2 0.1 0.05 0.025 25 dyues cm 15.4 15.014.9 15.1 15.1 16.8

2 corrected Cone. (wt. percent) 0.0125 0.0067 0.0033 0.0016 0.0008 20.922.3 26.3 34.7 41.3

25 dynes/cm 2 corrected The aqueous solutions of the above acids havebeen found to be particularly useful for extinguishing hydrocarbonfires.

EXAMPLE 6 Commercial vinyl acetate (containing 20 p.p.m. hydroquinone)was treated at C. for 10 min. with 1% by weight potassium hydroxidepellets, decanted and carefully distilled, B.P. 73, n 1.3923. Thedistilled material was kept cold, under nitrogen, until used.

A mixture of vinyl acetate (8.6 g., 0.10 mole), 1-iodoperfluoropropane(29.6 g., 0.1 mole) and a,a-aZobis-a, dimethylvaleronitrile (0.10 g.)was heated at reflux under a nitrogen atmosphere for two hours. Then asolution of 0.1 g. of the azonitrile and 10 g. of iodide was added andthe heating was continued for 3.5 hours at 75-78. Excess iodide andvinyl acetate were then removed from the product at 20 mm. pressure(13.6 g., 11 1.3298): The residue weighed 33.1 g. (87% conversion, 96%material recovery). The product C F CH CHlO cCH had a boiling point of46/1.5 mm. or 56/5 mm., n 1.3971. The product darkens on exposure to airand light.

Analysis.-Calcd. for C7F7H6O'2IZ C, 22.0; H, 1.58; F, 34.8; I, 33.2.Found: C, 22.4, 22.1; H, 1.5, 1.5; F, 34.4, 34.3; 1, 32.9.

10 EXAMPLE 7 A solution of C F CH CHIO CCH (81.0 g., 0.21 mole) in coldalcohol (100 ml.) was added over a period of one'hour to a rapidlystirred slurry of zinc dust (20 g.) in alcohol (50 ml.) heated at 60 C.The solution was saturated with dry hydrogen chloride at 15 min.intervals. An additionallO g. of zinc dust was added after threequartersof an hour and refluxing was continuedfor onehalf hour after theaddition was complete. The product was extracted with Water, the watersolution made alkaline and extracted with ether. The ether solution,after drying over anhydrous magnesium and calcium sulfates, wasdistilled giving C F CH CH OH, B.P. 125 or 75 mm., 11 1.3123, 28.7 g.(67% conversion), and C F CH CH O CCH B.P. 38-49/ 10 mm., 11 1.3282, 3.3g. (6.2% conversion). Park et al., J. Org. Chem., 23, 1166 (1958), havereported similar boiling points for these compounds.

When the reduction was carried out by standard techniques using lithiumaluminum hydride, a 72% yield of alcohol was obtained.

If the reduction is carried out using zinc in moist ether, the coupledproduct results. 7

EXAMPLE 8 (A) A mixture of B-pinene (27.2 g., 0.20 mole),l-iodoperfluoropropane (29.6 g., 0.10 mole) and u,oc'-aZ0biS u,-dirnethy1valeronitrile (0.5 g.) was heated at 50-6'0 C. for six hours(some exothermic reaction) giving a colorless reaction product.Unreacted materials were pumped 011 at 70/ 1 mm, giving 31.8 g. (74%conversion) of a light yellow liquid which solidified on cooling.Recrystallization of the solid from methylene chloride gave material,M.P. 3536.5 C. which was sensitive to light and air.

Analysis.--Calcd. for C H F I: C, 36.2; H, 3.7.; :F, 30.8; I, 29.4.Found: C, 36.1; H, 3.9; F, 30.2; I, 28.3.

The cold trap contained 17% of the C F I and 66% of the fl-pinenecharged.

The product from this reaction was not and bornyliodide, resulting fromloss of iodine and disproportionation of the initial addition product.The

and

1 1 bornyl iodide results from reaction of fi-pinene with hydrogeniodide. The products are characterized in the experiment below.

(C) A mixture of fi-pinene (40.8 g., 0.30 mole), l-iodoperfluoropropane(100 g., 0.33 mole) and benzoyl peroxide (1.0 g.) was charged into aHastelloy C tube, sealed and heated at 100 C. for 8 hours. The product(134 g.) was distilled giving CgFqI (75% recovery), B-pinene (50%recovery), a mixture of the pure materials were collected from thechromatogram. Analysis of benzene derivative.Calcd. for C H F C, 51.6;H, 4.34. Found: C, 52.0; H, 4.4.

Analysis of cyclohexane derivative. Calcd. for C H F C, 50.6; H, 6.2.Found: C, 51.7; H, 5.2.

EXAMPLE 9 and and 62% A mixture of norbornylene (bicyclo(2,2,l)heptene2) (9.4 g., 0.10 mole), l-iodoperfluoropropane (29.6 g., 0.10 mole) anda,oU-aZObis-rx,y-dimethylvaleronitrile (10.3 g., 1.2 mm.), was heatedunder nitrogen at 6080 C. for five hours. The product2-heptafluoropropyl-3-iodobicyclo(2,2,l)heptane (40.5 g., 100% recovery)was distilled giving a liquid (35.2 g., B.P. 105/20 mm., 111.4401-1.4406, conversion 90%, yield 100%). The cold trap contained 4.3g. starting materials.

Analysis.Calcd. for C H F I: C, 30.8; H, 2.58; F, 34.1; I, 32.6. Found:C, 30.8; H, 2.3; F, 36.7; I, 31.8.

The product appears to have the trans geometric configuration since HIcannot be removed readily by refluxing with alcoholic alkali nor bydistillation from concentrated aqueous alkali.

EXAMPLE A mixture of 16-heptadecenoic acid (13.5 g., 0.05 mole)l-iodoperfluoroheptane (25 g., 0.05 mole) anda,u'-azobisisobutyronitrile (0.1 g., 1.2 mm.) was heated at 80-100" C.for seven hours. The excess C F I was then removed giving 37.7 g. (98%)of crude -M.P. 47.5-49 C.

1.2 Analysis.Calcd. for C H F O I: F, 37.3; I, 16.6. Found: F, 35.0; I,15.9.

The above crude acid was treated with zinc in alcoholic hydrogenchloride (cf. Example 7) giving 7 15( z) rs z z s M.P. 53.5'58 in 100%recovery. Recrystallization from 95% alcohol raised the M.P. to 59-59.5C.

Analysis.--Calcd. for C26H37F15O2I C, 46.9; H, 5.60. Found: C, 46.9; H,5.3.

The ester was hydrolyzed with alcoholic potassium hydroxide which gave,on acidification, the free acid 7 1s 2) ie z M.P. 91.5-92.0 fromchloroform.

Analysis.Calcd. for C H F O C, 45.2; H, 5.21; F, 44.6. Found: C, 45.2;H, 5.5; F, 43.4.

Alcoholic solutions of the potassium salt of this acid did not wet glassbut rolled off like oil.

EXAMPLE 11 (A) A mixture of l-iodoperfluoropropane (0.33 mole),tri-chlorotrifiuoroethane (72 g.) and di-tert-butyl peroxide (6.5mmoles) was charged into 400 ml. Hastelloy C shaker tube. Ethylene (0.4mole) was compressed into the sealed shaker tube and the total mixturewas heated at 138-188 C. for eight hours. Distillation of the reactionmixture gave C F CH CH I in 87% conversion and 92% yield, B.P. /200 mm.,11 1.3767.

This compares well with B.P. 77.8/-185 mm, 11 1.3771 reported by Park etal. (J. Org. Chem., 23, 1166 1958)).

No telomer products containing more than one ethylene unit wereobtained.

(B) A mixture of l-iodorperfiuoropropane (0.1 mole) anda,a-azobisisobutyronitrile (0.5 g.) was charged into a shaker tube aspreviously described. Ethylene was then pressured into the tube. Thecontents were then heated at 80 C. for 8 hours. The product Was thendistilled. The experimental variables and composition of the prod netsare shown below.

. is From a similar series of reactions using C F I and C F I, thefollowing compounds were characterized.

Thus, it can be seen that products containing varying amounts ofethylene can be prepared by proper adjustment of reaction conditions.

EXAMPLE 12 A mixture of uninhibited vinyl acetate (prepared as describedin Example 6 (8.4 g., 0.1 mole), 1,6-diiodoperfluorohexane (20.0 g.,0.036 mole) and .a,u'-azobisisobutyronitrile (0.1 g.) was heated at87-130 for 3 hours. Conversion of iodide was essentially complete (26.6g. product). The product,

CH CO CHICH CF CF CH CHIO CCH was a solid which was not stable todistillation.

Analysis.Calcd. for C H F O I C, 23.1; H, 1.66; F, 31.3; I, 34.9. Found:C, 24.5; H, 2.4; F, 30.2; I, 33.5.

A mixture of the above product (24 g.), zinc g.) and acetic acid (75%,100 ml.) was heated at SO-65 C. for 1 hour while anhydrous hydrogenchloride was added periodically. The reaction mixture was drowned inwater, neutralized and extracted with ether. After drying the ethersolution Was distilled giving a liquid, B.P. 123-1125 /0.8 mm., 7.2 g.The infrared spectrum indicated the product to be a mixture of acetateand alcohol. Heating with acetic anhydride gave after distillation 7.2g. of pure diacetate (no OH band in IR), B.P. 10'4/ 0.1 mm., n 1.3698.

Analysis.Calcd. for C H F O C, 35.4; H, 3.0; F, 48.10. Found: C, 35.4;H, 3.0; F, 47.8.

EXAMPLE 13 A mixture of l-iodoperfluoroundecane (11.0 g., 0.016 mole),uninhibited vinyl acetate (see Example 6, 3.0 g., 0.035 mole) anda,a'-azobisisobutyronitrile (0.1 g.) was heated at 74-80 C. for 7 hours.The product (13.3 g., 100% recovery) was an impure solid, M.P. 75-83 C.Recrystallization of a small amount from methylene chloride gave aprecipitated-gel of C F CH CHIO CCH M.P. 88-107".

Analysisr-Calcd. for C H F O I: C, 23.0; H; 0.8. Found: C, 23.7; H, 1.1.

A mixture of C F CH CHIO CCH (10 g., 0.013 mole), zinc (10 g.) and 75%aqueous acetic acid (50 cc.) were heated together for 1 hour. Recoveryof the product as previously described gave C F CH CH OH, (5.0 g.), M.P.108-110"; and an ether and chloroform insoluble solid (1.5 g.) meltingrange 94117.

Analysis.-Calcd. for C H F O: C, 25.4; H, 0.8; F, 71.1. Found: C, 25.8;H, 1.4; F, 70.4.

EXAMPLE 14 A mixture of 1-iodo-4-hydroperfluorobutane (20.8 g., 0.1mole), uninhibited vinyl acetate (see Example 6, 6.0 g., 0.12 mole)a,on-azobis-n y-dimethylvaleronitrile (0.8 mmole) and 0:,04'azobisisobutyronitrile (0.6 mmole), was heated at 7092 C. for 12 hours.The crude product weighed 25.2 g. (100% recovery). The conversion was88% and the yield of H(CF CH CHIO CCH was greater than 90%.

Analysis.-Calcd. for C8H7F4O2I: C, 23.2; H, 1.7; F,

I 36.7; I, 31.4. Found: C, 25.5; H, 2.7; F, 33.0; I, 29.3.

The crude product could not be distilled, but it was reduced by heating24 g. (0.052 mole) with zinc (10 g.), 100 ml. of ethanol and 10 ml. ofconcentrated hydrochloric acid at 5660 C. The reaction mixture wasdrowned in water and extracted with chloroform. Distillation of the drychloroform solution gave B.P. 71/15 mm., n 1.3322, 6.7 g., 51% yield.

Analysis.Calcd. for C H F O: C, 29.3; H, 2.5; F,

62.1. Found: C, 29.7; H, 2.7; F, 61.9.

A second unknown fraction, B.P. 90102/0.6 mm., n 1.3678. Found: C, 32.8;H, 2.8; F, 56.4; 3.3 g. (25%) was also obtained.

EXAMPLE 15 A mixture of l-iodoperfiuoroheptane (0.1 mole), uninhibitedvinyl acetate (0.1 mole) and a,a-azobisis'obutyronitrile (0.1 g.) washeated under nitrogen at 70- 80 C. for 5 hours. Then 4.0 g. ofperfiuoroheptyl iodide and 0.1 g. of azonitrile were added and heatingwas continued for two hours (the reaction is somewhat exothermic).Excess C'1F15I was pumped off at 60/8 mm. leaving 57.4 g. of liquidresidue Analysis.Calcd. for C H F O I: C, 22.7; H, 1.0; F, 48.9; I,21.8. Found: C, 24.2; H, 1.5; F, 49.1; I, 20.9.

The crude iodoacetate (55 g., 0.095 mole) was dissolved in ml. of 95%ethanol and this solution Was added over a one hour period to a slurryof Zinc dust (20 g., 0.30 mole) in 95% ethanol ml.) and 10 ml. ofconcentrated hydrochloric acid at 60 C. while stirring rapidly. Two, 5ml. portions of hydrochloric acid were added during the period ofaddition. After addition, the mixture was stirred for one hour, cooledto 25 C. and diluted with water (100 ml.). The oil layer was collected(36.6 g.) and the aqueous layer was extracted with chloroform.Distillation of the combined solutions gave 39.7 g. (95 of crude productwhich was then heated at 60 C. for one hour with 50 ml. of 10% ethanolicpotassium hydroxide. The mixture was drowned in water, and extractedinto chloroform, which, after drying over magnesium sulfate, wasdistilled giving B.P. 84/l0 mm., 11 1.3164.

AnaIysis.-Calcd. for C H F O: C, 26.2; H, 1.2. Found: C, 26.4; H, 1.6.

An infrared band was present at 2.95 due to hydroxyl group.

EXAMPLES 16 TO 68 Theseexamples were carried out in manners analogous tothe examples already described. The details are indicated in Tables Iand II which follow.

633 mo 98 33503 3w :wO n O m Q 3A on 236 uo fioxfio 2 2 8 i Z Q I. Hrdobzo mo o mo a m mo m0 "WU a ma wfio flowo/ w cww NA Zm 1c mo ocanoa E mzion}... R "HO 3 #v Q Q HHOHO QEOV S ow fi. a; m4 To H6 e fi emon-500 on5wmfim 6 naA om {owl-lw owAK m Zmaw H o H o 0% w 'mm 5 M50556 i Q2 3:3 33 u w 2. Q m Nd Nd E i on n mm .iam mm m h 3A5 w A m m o m d EHQGOE 338m $558 1H \llll GA 2 E0 w 215 N H Z H o m o 31 Qmmgw nw dm298 fi m mm3A 3 Q6 3 3 9m .HMEQ To H6 E AH 388 386 on 4m HI 3A 3 :10 w. 5 c4 0M4 H6Md wfio oawvdmo oho on3 mmfim 3 HI i n HU om mm Tm Z N6 N6 -5 n 33 226-4 2 I m m 2 m: 754 H6 o H -O {5.1.21.11-2.1.1....IE2O F0 11 m h moflflOHmo mo h o om omw fl m Zm Hd To Qm AH 258 32 H1O NA zmjw .l: owlowl QH O HHHO HHORHO EHOV 3 E16 0 Z H o H o FH RP 0v onoamm m 553 2 $852Awv 33% 458 E 00 EH2 388m 052 232: 356. dfir 38m. HE 3 HE 520 uo vg M225 mZOHBnZdHMH Sa b 8 HH m ooH o mo m o n 8 3 N H Z HH 5 H d H H5 m o oomo 2. HH 3 H HHO OHO HHO EO @H 8 3 Hz 2M3 H6 and H rfio mo oo omo 27---2 m 8 HH moa OHO MOE Q w on H Z H NH Hado H05 o omo 8 m-w HH 3 2 qmooflo aH o min H; Z Ha Ha HrH o mwm 8 3 8H m O Q WH VH MHO EO H; 02H H o754 8 0 v3 d do -Hw oofimovo om 8 H10 8 N 8 3 H= H P L HHG w EH3 H N ZmH d H d Hrflo mo o mdo H 52334 0332153 .HB on o .H Z :7. 8A @H ZoqHoHmomorfio NH Him A i N d H o EHG zo momo mo 3 No 8 Ha oo H o mofifiHorm 3 2w o 2%. 8 Q 2:. Hfimorm 8 :8...: 8 mm mOUSHmQ MQAQQHO b $8 w H 25 H o Ho EwH 0:0 83 35 8 5:8 um 3 S Hfloo cmovmozrm 036 8 H H P HH "IR-O 8EHOSO QHHQEOA HH oEHo 8 8 6 M aw 5% 8 SH 556 o cmHovHmo mHomofim OFHO m78 d 754 S e no Hmofimovo 8 3 mm H OH H H HE v 8 H E H HH m m QHH VAQOWHHO QM 0v 8 i A A .6 ofimozmo mo o 55E: 2 5 N H 25 ms 0 n2 6 13HOXHQFH 9 1 2 25m 5: cm H OEQWOEQ W H v B H D E E E. m H H OOHQMOVAQO mOHQMUV 8 8 6 m 3A A ofimovHmo mHoim0502 m 0v 2 $2. m H $2 EH: x v.. v 225m E: cw S coufifiwhm H 8 8 6 m 8A a mo o cmovHmo moxfH oZH o FH 9 HH 22. N H Z5 8 0 8d QfimoEofim 0v 555 ofimovmofi mo o wm ozmo mo rdomzfiomzow imovmo fio E. 2. T F O H Fd m fi wH 2E H 0 H6 Hrfio o o wz aomz w mo mo 3 2 nmao o A p m m m NHHH H l HHOHNOL. MHOHH n co m .H 2mg 2o 2 o .QHMHOAH oHHEEw nzwom 3 3 2 3 E2. 250 .3 EH20 anofiom 253mm 233:3.5 685. :HHEPH EN 62 HJH H620 9302 wfi :5 uowafi o mzcpodfim QE S m uTable lIContinued PRODUCTS-Continued Analysis Example N 0. Productb.p./mm. m. Calculated Found H F I O H F I 59 11-C4F9C F-CHCHI(CHz)sCOzC2Ei5 Oil 1.4041 34. 7 3. 7 37. 19.3 36. 0 4. 4 19.1

11-041 9? F(CH:)mCOzCnH5 129/1. 0 1.3743 42. 9 4. 7 43. 3 4. 5

n-C4FoCI F(C.Hz)1oC 01H 150/1. 0 1. 3761 40. 5 4. 2 49. 0 40. 8 4. 1 48.3

60 OKCFahCHaGHIOzCCH: 32/01 1. 4404 20. 7 1. 7 1062 36. 4 21. 4 1. 9 10611 36. 4 61 Br(CFa)2CH1CHIOzCCHa 42/0. 3 1. 4609 18. 3 1. 5 19. 4 32. 319. 0 1. 9 62 n-CaF7CH CHICHqCN 47/0. 2 1. 4148 23. 2 1. 4 36. 6 N 3. 924. 1 1. 5 36. 2 N 4. 6

l' I 63 n-C;F1-CHC I 11-1 50/06 1. 4802 31. 9 30.9 L 1 J n=2 1.5409 25.423.5

C5115 m V MYV, Calc't 500; Found, 508.

64 11-C5F7CH=CI(CHn)aCOzH 011 1.4442 27.8 26.5 25.8 25.9 65Il-C3F7-C|3=CIC2H5 0i] 1. 4317 33. 5 28. 8

CgH5

66 I1C3F7CH=CICO7CH3 42/2 4098 22. 1 1. 1 35. 0 33. 4 22. 3 1. 6 36. 933. 9 67 58/1 1. 3817 22. 8 0. 69 49. 2 23. 0 23. 0 0. 7 49. 0 22. 1n-C1F CH=CIC 0 H 130/1 1 57-61 1 M.P., degrees. 3 Viscous oil. IPolymer, viscous oll.

"'CqHa.

EXAMPLE 69 Sodium hydroxide (8.0 g., 0.2 mole) was added over a periodof one-half hour (while protected from the atmosphere) to a stirredsolution of (41 g., 0.1 mole, see Examples 30 to 32) in 100 ml. of etherat 24 C. (some heat produced). When the addition was complete themixture was stirred and heated under reflux for five hours, the solutionbecoming orange during that period. The solid material was thencollected by filtration and washed withether (22.8 g. of solid). Thecombined ether solutions were distilled givmg C F CH=CI( CH c0 11 as thesodium salts are as follows:

(11) Cone. (wt. percent) 0.40 0.20 0.10 0.05 0.025 (1))7 25 dynes/em20.3 20.9 23.2 25.7 I 27.?

corrected (a) Cone. (wt. percent) 0. 014 0.007 0.0035 0. 0006 28. 5 28.629.8 32.0

(1))7 dynes/cm 2O corrected It is readily apparent that the presentprocess is less time consuming than either the thermal or photochemicalprocesses and that products can be prepared by this process which cannotbe prepared by either the thermal or photochemical processes, e.g., R;CHCHIO CCH This process is also much more readily carried out in acontinuous manner than the thermal or photochemical processes.

It is understood that the preceding representative examples may bevaried, within the total present disclosure as understood and practicedby one skilled in the art, and substantially the same results obtained.

As many apparently widely dilferent embodiments of this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that this invention is not limited to the specificembodiments thereof except as defined in the appended claims.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A composition having the structure F(C,,F ,,)Q wherein Y is selectedfrom the group consisting of hydrogen, fluorine, chlorine and bromine, nis an integer from one to about twenty and Q is selected from the groupconsisting of (a) CH CHIO CR and (e) CH=CI(CH CO H wherein R of (a) is alower alkyl group and m of (b), (c), (d) and (e) is an integer of fromzero to about fourteen.

2. A composition having the structure F (0,1 CH CHIO CCH 3. Acomposition having the structure F(C F CH CHIO CCH 4. A compositionhaving the structure F(C F CH CI-IICH 0(CH CO H 5. A composition havingthe structure F (C7F14) ZCOZH 6. A composition having the structure F(C7F14) CH CH CH O (CH CO H 7. A process for reacting a polyfluoroalkyliodide with a reactant taken from the group consisting of aliphaticolefins and acetylenes, said iodide having the structure selected fromthe group consisting of ACFIB and I(C F- )I, said A and B being selectedfrom the group consisting of F and Y(C F said Y being selected from thegroup consisting of F, Cl, Br, and H, said r being from 3 to about 20and said It being from about 1 to about 20, said process being onewherein said polyfluoroalkyl iodide is reacted with an unsaturatedcompound taken from the group consisting of an aliphatic olefin, and anacetylene compound, said heating step being conducted 15 at atemperature in the range of from about 50 C. to

about 190 C. in the presence of a free radical generating compoundselected from the group consisting of organic peroxides and organic:azonitriles at a pressure of from about 1 to about 50 atmospheres,followed by re- 5 covering the reaction product.

References Cited in the file of this patent UNITED STATES PATENTS2,858,331 Fenske et a1 Oct. 28, 1958 10 2,972,638 Tiers Feb. 21, 19612,975,220 Hauptschein et a1 Mar. 14, 1961 OTHER REFERENCES Henne: I. Am.Chem. Soc. 73, 1791-1792 (1951). Haszeldine et al.: J. Chem. Soc.(London), 1953, 1199-1206.

1. A COMPOSITION HAVING THE STRUCTURE F(CNF2N)Q WHEREIN Y IS SELECTEDFROM THE GROUP CONSISTING OF HYDROGEN, FLOURINE, CHLORINE AND BROMINE, NIS AN INTEGER FROM ONE TO ABOUT TWENTY AND Q IS SELECTED FROM THE GROUPCONSISTING OF (A) -CH2CHIO2CR
 7. A PROCESS FOR REACTING APOLYFLUOROALKYL IODIDE WITH A REACTANT TAKEN FROM THE GROUP CONSISTINGOF ALIPHATIC OLEFINS AND ACETYLENES, SAID IODIDE HAVING THE STRUCTURESELECTED FROM THE GROUP CONSISTING OF A-CFI-B AND I(C7F2R)I, SAID A ANDB BEING SELECTED FROM THE GROUP CONSISTING OF F AND Y(CNF2N), SAID YBEING SELECTED FROM THE GROUP CONSISTING OF F, CI, BR, AND H, SAID RBEING FROM 3 TO ABOUT 20 AND SAID N BEING FROM ABOUT 1 TO ABOUT 20, SAIDPROCESS BEING ONE WHEREIN SAID POLYFLUOROALKYL IODIDE IS REACTED WITH ANUNSATURATED COMPOUND TAKEN FROM THE GROUP CONSISTING OF AN ALIPHATICOLEFIN, AND AN ACETYLENE COMPOUND, SAID HEATING STEP BEING CONDUCTED ATA TEMPERATURE IN THE RANGE OF FROM ABOUT 50*C. TO ABOUT 190*C. IN THEPRESENCE OF A FREE RADICAL GENERATING COMPOUND SELECTED FROM THE GROUPCONSISTING OF ORGANIC PEROXIDES AND ORGANIC AZONITRILES AT A PRESSURE OFFROM ABOUT 1 TO ABOUT 50 ATMOSPHERES, FOLLOWED BY RECOVERING THEREACTION PRODUCT.